Process for Removal of Hydrogen Sulfide in Downhole Oilfield Applications

ABSTRACT

A method and system remove hydrogen sulfide from a sour liquid. In an embodiment, the method for removing hydrogen sulfide from a hydrocarbon containing fluid includes contacting a methylmorpholine-N-oxide solution with the sour liquid. The method also includes allowing the methylmorpholine-N-oxide to react with the hydrogen sulfide to remove the hydrogen sulfide.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.14/630,244 filed on Feb. 24, 2015, which is a continuation of U.S. Pat.No. 8,993,488 issued on Mar. 31, 2015, which is a non-provisionalapplication that claims the benefit of U.S. Application Ser. No.61/446,117 filed on Feb. 24, 2011, the entire disclosures of which areincorporated by reference herein in their entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

BACKGROUND OF THE INVENTION Field of the Invention

This invention relates to the field of hydrocarbon production processesand more specifically to removal of hydrogen sulfide in downhole oil andgas field applications.

Background of the Invention

During the drilling, production, and transportation of crude oil,hazardous hydrogen sulfide may often be encountered in many hydrocarboncontaining fluids. For instance, when crude oil is extracted, it istypically in contact with water and gas. During downstream separation ofthe oil and water, hydrogen sulfide may be released as a gas from theassociated oil and water phases. Hydrogen sulfide may pose healthhazards as well as corrosion issues and potential reactions with otherhydrocarbons.

Numerous approaches to these problems have been developed. Suchdevelopments to control hydrogen sulfide downhole include solidscavengers (i.e., such as zinc oxide or other metal oxides) forcomplexing hydrogen sulfide in solid form, liquid scavengers (i.e., suchas amines, morpholine, or acrolein) for complexing hydrogen sulfide inliquid form, and oxidizing chemicals (i.e., mild oxidizers such asnitrite or long-chain amine oxides and strong oxidizers such asperoxides) that convert hydrogen sulfide to more harmless forms ofsulfur such as elemental sulfur or thiosulfate.

There are drawbacks to these developments. For instance, metal oxidesolid scavengers generally react reversibly with hydrogen sulfide. As aresult, there is a risk of regeneration of hydrogen sulfide if pHchanges are experienced during subsequent handling of the reactionproduct. Liquid scavengers may be cost effective and tie up hydrogensulfide as water soluble compounds that may be discharged to wastewatertreatment facilities. Some of these scavengers (i.e., acrolein) may tieup hydrogen sulfide in an irreversible manner. Other liquid scavengers(i.e., some amines) react with hydrogen sulfide reversibly, so there ispotential for the re-evolution of hydrogen sulfide in subsequenthandling. Oxidizing chemicals may irreversibly convert hydrogen sulfideto harmless water soluble forms of sulfur that are compatible witheffluent discharge. However, there are several potential complicationswith these chemicals. Long chain amine oxides may produce foaming due totheir surfactancy and may involve large treatment volumes and/or cost inoilfield applications. These amine oxides also typically have limitedefficiency for large amounts of hydrogen sulfide since they are normallydiluted in water to prevent gel formation. Oxidation using nitrites mayproduce ammonia as a by-product that may, in turn, potentially stall thesulfide oxidation before it is complete. The nitrite oxidation reactionmay also be accompanied by a rise in pH, which may cease the oxidationbefore it is complete. Stronger oxidizers, such as permanganate orperoxides, may be quite non-selective in their reaction and may bereactive with many of the hydrocarbon components that exist downhole.For instance, strong oxidizers may react with hydrocarbon components incrude oil and may also generate harmful reaction products such aschlorine in the case of hypochlorite. Permanganate may produce solidmanganese dioxide as a reaction product, which may be inefficient foroilfield operations and may be especially prohibitive in downholeapplications where the reaction product may pose plugging issues.Peroxide is typically very temperature sensitive and may decomposerapidly at elevated temperatures and a pH above 7, which are verytypical in oilfield applications.

Consequently, there is a need for an improved method for removinghydrogen sulfide from hydrocarbon containing fluids.

BRIEF SUMMARY OF SOME OF THE PREFERRED EMBODIMENTS

These and other needs in the art are addressed in an embodiment by amethod for removing hydrogen sulfide from a hydrocarbon containingfluid. The method includes contacting a methylmorpholine-N-oxidesolution with the hydrocarbon containing fluid. The method also includesallowing the methylmorpholine-N-oxide to react with the hydrogen sulfideto remove the hydrogen sulfide.

The foregoing has outlined rather broadly the features and technicaladvantages of the present invention in order that the detaileddescription of the invention that follows may be better understood.Additional features and advantages of the invention will be describedhereinafter that form the subject of the claims of the invention. Itshould be appreciated by those skilled in the art that the conceptionand the specific embodiments disclosed may be readily utilized as abasis for modifying or designing other embodiments for carrying out thesame purposes of the present invention. It should also be realized bythose skilled in the art that such equivalent embodiments do not departfrom the spirit and scope of the invention as set forth in the appendedclaims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In an embodiment, a hydrogen sulfide removal process includes contactinghydrogen sulfide with methylmorpholine-N-oxide. Without limitation, thehydrogen sulfide removal process may remove hazardous hydrogen sulfidesin downhole applications such that the hydrocarbon containing fluids(i.e., oil) have reduced amounts of hydrogen sulfide after treatment. Inembodiments, sour liquid or gas containing hydrogen sulfide is contactedwith a methylmorpholine-N-oxide solution, which removes hydrogen sulfidefrom the liquid or gas by oxidation to produce elemental sulfur. In someembodiments, the methylmorpholine-N-oxide solution irreversibly removeshydrogen sulfide from the liquid or gas by oxidation to produceelemental sulfur. Without limitation, the oxidation may thwart the riskof subsequent regeneration of hydrogen sulfide during handling of theproduct (i.e., the produced hydrocarbon containing fluid). Inembodiments, the oxidation mechanism may be a mild mechanism so thatcomplicating side reactions with hydrocarbon components may beminimized. It is to be understood that a mild oxidation mechanism refersto that which is too weak to bring about oxidation of hydrocarbons.Moreover, in some embodiments, the methylmorpholine-N-oxide may notproduce excessive foaming.

In an embodiment, the methylmorpholine-N-oxide solution includesmethylmorpholine-N-oxide and water. The methylmorpholine-N-oxidesolution may have any wt. % of methylmorpholine-N-oxide suitable forirreversibly reacting with the hydrogen sulfide to produce elementalsulfur. In an embodiment, the methylmorpholine-N-oxide solution hasbetween about 1.0 wt. % methylmorpholine-N-oxide and about 60.0 wt. %methylmorpholine-N-oxide, alternatively between about 50.0 wt. %methylmorpholine-N-oxide and about 60.0 wt. % methylmorpholine-N-oxide.In some embodiments, the methylmorpholine-N-oxide solution includesadditives. Without limitation, examples of additives includesurfactants, pH adjustment chemicals, dyes, or any combinations thereof.

In embodiments, the reaction between the methylmorpholine-N-oxide in themethylmorpholine-N-oxide solution and the hydrogen sulfide in thehydrocarbon containing fluid is catalyzed by iron. Any amount of ironmay be present that is suitable to catalyze the reaction. In anembodiment, the hydrogen sulfide removal process includes between about10 ppm and about 50 ppm of iron. In an embodiment, the iron compriseshydrated ferrous salt, hydrated rust, or any combinations thereof. Insome embodiments, the iron is provided by rust disposed downhole.

In embodiments, the hydrogen sulfide removal process includes theaddition of heat to the methylmorpholine-N-oxide solution. The heat maybe added by any suitable means such as by subterranean heat, steam, hotwater, or any combinations thereof. In an embodiment, the heat is addedby subterranean heat. It is to be understood that subterranean heatrefers to the natural heat present in subterranean depths. Themethylmorpholine-N-oxide solution may be heated to any temperaturesuitable for increasing the reaction between themethylmorpholine-N-oxide and the hydrogen sulfide. In an embodiment, themethylmorpholine-N-oxide solution is heated to a temperature betweenabout 40° C. and about 75° C., alternatively between about 40° C. andabout 60° C., and alternatively between about 40° C. and about 50° C.,and further alternatively about 50° C. In an embodiment, the heat isadded to facilitate the reaction between the methylmorpholine-N-oxideand the hydrogen sulfide. In embodiments, further heat is added toincrease the reaction rate. Without being limited by theory, thesubterranean heat has a corresponding temperature increase as the depthsincrease, and such increased temperatures may increase the reaction ratebetween the methylmorpholine-N-oxide and the hydrogen sulfide. Further,without being limited by theory, a temperature increase is experiencedof about 1.6° F. for about every 100 feet downhole. In some embodiments,the methylmorpholine-N-oxide solution may be stable up to temperaturesexceeding 270° F., which may be advantageous for downhole applicationswhere the temperature may reach about 250° F. at a 10,000 foot depth.

Any suitable timeframe in which the methylmorpholine-N-oxide solution isexposed to the hydrogen sulfide that allows for removal of hydrogensulfide may be used. In an embodiment, the timeframe is from about 24hours to about 48 hours. In alternative embodiments, the time frame isfrom about 24 hours to about 30 hours.

In embodiments, the methylmorpholine-N-oxide solution may be added insuitable amounts to provide a suitable ratio of methylmorpholine-N-oxideto hydrogen sulfide that removes hydrogen sulfide. In embodiments, themethylmorpholine-N-oxide to hydrogen sulfide ratio is about a 5:1 moleratio of methylmorpholine-N-oxide to hydrogen sulfide, alternativelyabout a 4:1 mole ratio of methylmorpholine-N-oxide to hydrogen sulfide,and alternatively about a 3:1 mole ratio of methylmorpholine-N-oxide tohydrogen sulfide, and further alternatively about a 2:1 mole ratio ofmethylmorpholine-N-oxide to hydrogen sulfide, and alternatively about a1:1 mole ratio of methylmorpholine-N-oxide to hydrogen sulfide. In anembodiment, the methylmorpholine-N-oxide to hydrogen sulfide ratio isabout 2:1. Embodiments include a methylmorpholine-N-oxide to hydrogensulfide mole ratio between about 1:1 and about 5:1, alternativelybetween about 1:1 and about 4:1, and alternatively between about 1:1 andabout 3:1, and further alternatively between about 1:1 and about 2:1,and also alternatively between about 2:1 and about 3:1. In anembodiment, the methylmorpholine-N-oxide to hydrogen sulfide mole ratiois between about 1:1 and about 2.5:1.

The methylmorpholine-N-oxide solution may be injected downhole by anysuitable delivery method. In embodiments, the delivery method includespumping the methylmorpholine-N-oxide solution into the drilling fluid,injecting the methylmorpholine-N-oxide solution with steam (and theninto the drilling fluid), or any combinations thereof. In embodiments,the methylmorpholine-N-oxide solution may be pumped into the drillingfluid at suitable injection points. In embodiments, injection pointsinclude injection directly into the annulus, injection through the drillstem, injection at the beginning of the horizontal leg, or anycombinations thereof. In embodiments, the steam is a 150 psig steam orless. In an embodiment, the steam is about 50 psig steam, alternativelybetween about 50 psig and about 150 psig steam.

Without being limited by theory, the hydrogen sulfide removal processprovides the methylmorpholine-N-oxide as a weak oxidizer, which mayavoid side reactions with hydrocarbons and that also may ensure thathydrogen sulfide may not be regenerated during downstream handling.Further, without being limited by theory, the hydrogen sulfide removalprocess may exhibit limited foaming relative to longer chain amineoxides, which have stronger surfactant properties. Moreover, withoutbeing limited by theory, the hydrogen sulfide removal process hastemperature stability, which may be more versatile in various oilfieldenvironments such as downhole injection. In addition, without beinglimited by theory, the hydrogen sulfide removal process may not produceharmful by-products during the treatment. Additionally, without beinglimited by theory, similar to long-chain amine oxides, the reactionproduct of methylmorpholine-N-oxide is an amine. However, unlikelonger-chain amine oxides, the amine reaction product ofmethylmorpholine-N-oxide is water soluble rather than oil soluble.Therefore, downstream processing may be facilitated because theconsequence is limited amounts of nitrogen compound introduced into thehydrocarbon product. Such nitrogen compounds may be catalyst poisons inmany refining processes.

In some embodiments, the hydrogen sulfide removal process includestreating a portion or substantially all of the solid elemental sulfurdeposits produced by the reaction of the methylmorpholine-N-oxide withhydrogen sulfide. The elemental sulfur deposits may be treated by anysuitable method. In an embodiment, the elemental sulfur deposits aretreated by dissolving the elemental sulfur. The solid elemental sulfurdeposits may be dissolved by any suitable methods. In embodiments,dissolving additives are added to dissolve the solid elemental sulfurdeposits. In an embodiment, the dissolving additives include dimethyldisulfide, aqueous caustic soda, alkyl amine, or any combinations. In anembodiment, dimethyl disulfide is added to dissolve the solid elementalsulfur deposits. Any amounts of the dissolving additives may be addedthat are suitable for dissolving a portion or substantially all of thesolid elemental sulfur.

The hydrocarbon containing fluid may be a liquid or a gas. An example ofsuch a liquid is oil. An example of such a gas is natural gas.

To further illustrate various illustrative embodiments of the presentinvention, the following examples are provided.

Example 1

A purpose of this example was to determine the extent of reaction ofmethylmorpholine-N-oxide on hydrogen sulfide in sour water at varyingmole ratios. The experiments were conducted at 40° C. and 60° C.

A pint of sour water at pH-8.5 was used. The hydrogen sulfide content ofthe sour water was analyzed at 9,985 mg/liter (0.293 M/lit). The solidmethylmorpholine-N-oxide used had a molecular weight of 126.0. Themethylmorpholine-N-oxide had some water of hydration.

The methylmorpholine-N-oxide stock solution was prepared by dissolving5.00 grams of methylmorpholine-N-oxide in 100.0 mls distilled water(0.397 M/lit). To each of several screw-capped sample vials, 2.0 mls ofthe sour water was added and a “dash” of powdered iron rust was added ascatalyst for the reaction. The vials were then diluted with ˜15 mls ofdistilled water and the following volumes as shown in Table 1 ofmethylmorpholine-N-oxide were added.

TABLE 1 Sample Makeup [methylmorpholine-N-oxide] = 0.397M/lit [hydrogensulfide] = 0.293M/lit (@ pH~8.5) ~0.5 gm Fe₂O₃•xH₂O as catalyst VolumeMole ratio (methylmorpholine- methylmorpholine-N-oxide N-oxide:hydrogensulfide) 1.477 mls 1.0:1 1.772 mls 1.2:1 2.067 mls 1.4:1 2.363 mls 1.6:12.658 mls 1.8:1 2.953 mls 2.0:1 4.430 mls 3.0:1

Three of such series were prepared. Each series was treated as follows:

Series 1: heated at 40° C. for 24 hours (static);

Series 2: heated at 40° C. for 48 hours (static); and

Series 3: heated at 60° C. for 24 hours (static).

At termination of the reaction periods, the entire contents of eachreaction vial were emptied into 20 mls of sulfide anti-oxidant bufferand titrated each with 0.100 M/lit Pb⁺⁺, according to ULI ProcedureLP1005. The results are shown below in Table 2.

TABLE 2 Reaction of methylmorpholine-N-oxide on hydrogen sulfide for 24Hours @ 40° C. Grams hydrogen Grams hydrogen Sample mls Pb⁺⁺ sulfidetitrated sulfide added % Reacted 1.0:1 1.9 0.00019 0.000585 68% 1.2:11.8 0.00018 0.000585 69% 1.4:1 1.7 0.00017 0.000585 71% 1.6:1 0.70.00007 0.000585 88% 1.8:1 0.4 0.00004 0.000585 93% 2.0:1 0.3 0.000030.000585 95% 3.0:1 0.0 0.00000 0.000585 100% 

TABLE 3 Reaction of methylmorpholine-N-oxide on hydrogen sulfide for 48Hours @ 40° C. Grams hydrogen Grams hydrogen Sample mls Pb⁺⁺ sulfidetitrated sulfide added % Reacted 1.0:1 0.4 0.00004 0.000585  93% 1.2:10.0 0.00000 0.000585 100% 1.4:1 0.0 0.00000 0.000585 100% 1.6:1 0.00.00000 0.000585 100% 1.8:1 0.0 0.00000 0.000585 100% 2.0:1 0.0 0.000000.000585 100% 3.0:1 0.0 0.00000 0.000585 100%

Elemental sulfur, present as small platelets, had been precipitatedduring reaction.

TABLE 4 Reaction of methylmorpholine-N-oxide on hydrogen sulfide for 24Hours @ 60° C. Grams hydrogen Grams hydrogen Sample mls Pb⁺⁺ sulfidetitrated sulfide added % Reacted 1.0:1 0.0 0.00000 0.000585 100% 1.2:10.0 0.00000 0.000585 100% 1.4:1 0.0 0.00000 0.000585 100% 1.6:1 0.00.00000 0.000585 100% 1.8:1 0.0 0.00000 0.000585 100% 2.0:1 0.0 0.000000.000585 100% 3.0:1 0.0 0.00000 0.000585 100%

Elemental sulfur, present as small platelets, had been precipitatedduring reaction.

Conclusions

At all mole ratios (methylmorpholine-N-oxide:hydrogen sulfide) down toand including 1:0:1.0, the destruction of hydrogen sulfide was completeat 60° C. after 24 hours. Elemental sulfur was a visible product. ThisS° was present as platelets (“flakes”).

After 24 hours at 40° C., the reaction was complete only at a mole ratioof 3.0:1.0, although nearly complete reactions were recorded at ratiosof 2.0:1.0 and 1.8:1.0. Reactions at lower mole ratios were variouslyincomplete and consistent with the lower loadings.

After 48 hours at 40° C., the reaction was complete at all mole ratiosexcept for the lowest loading (1.0:1.0). The product S° was variouslypresent as a milky suspension and flaked solids.

Example 2

Lab evaluations were aimed at defining the time requirements forcomplete eradication of hydrogen sulfide in a tank at different doselevels. The hydrogen sulfide content of the tank was 2% as estimated bya Chemets colorimetric test. The sample was analyzed by titration ofhydrogen sulfide with lead acetate, which showed hydrogen sulfide levelsat 3.85%.

For dosing studies, 1-ml samples of the tank's sour water were dilutedto 10 ml with deionized water. Various amounts of amethylmorpholine-N-oxide solution were added, and the samples placed ina water bath at 50° C. The methylmorpholine-N-oxide solution was 50 wt.% methylmorpholine-N-oxide. Each sample contained 0.0011 mole hydrogensulfide based on a 3.85% hydrogen sulfide content determined by leadacetate titration. Visual and other testing results during the course ofthe time study are summarized below in Table 5.

TABLE 5 mls of 0 0.35 0.5 0.7 0.8 methylmorpholine-N- oxide solutionmole ratio 0 {Control} 1:1 1.5:1 2:1 2.5:1 methylmorpholine-N-oxide:hydrogen sulfide Visible Visible Visible Visible Time Lapse (Hrs)Result Result Result Visible Result Result  8 Yellow Yellow Yellow DarkYellow Dark Solution Solution Solution Solution Yellow Solution 24Yellow Yellow Dark Clear Solution Clear Solution Solution Yellow WhitePPT Solution Blk PbAc Chemet Solution 0 hydrogen sulfide White test 600Chemet PbAc PPT Chemet <60 0 >600 hydrogen sulfide PbAc 28 Yellow YellowCloudy — — Solution Solution Yellow 30 Yellow Yellow Clear — — SolutionSolution Solution + White PPT 48 Yellow Dark — — — Solution YellowSolution Chemet 60-120 hydrogen sulfide 54 Yellow Cloudy — — — SolutionYellow Chemet <60 72 Yellow Clear — — — Solution Solution + White PPT 0hydrogen sulfide PbAc

Conclusion

Lab studies revealed that using original field conditions at the tank(50° C.), treatment times of less than 24 hours were achieved using amole ratio of 2:1. Dose rates as low as 1:1 also produced completeeradication of hydrogen sulfide albeit at longer reaction times (54-72hrs). Use of a 2:1 dose rate of methylmorpholine-N-oxide solutionprovided a cheaper alternative to potassium permanganate. A 3:1 doserate provided equivalent cost.

Although the present invention and its advantages have been described indetail, it should be understood that various changes, substitutions andalterations may be made herein without departing from the spirit andscope of the invention as defined by the appended claims.

What is claimed is:
 1. A method for removing hydrogen sulfide from asour liquid comprises: (A) contacting a methylmorpholine-N-oxidesolution with the sour liquid; (B) adding heat to themethylmorpholine-N-oxide solution; and (C) allowing themethylmorpholine-N-oxide to react with the hydrogen sulfide to removethe hydrogen sulfide.
 2. The method of claim 1, wherein themethylmorpholine-N-oxide solution comprises methylmorpholine-N-oxide andwater.
 3. The method of claim 1, wherein the methylmorpholine-N-oxidesolution comprises between about 1.0 wt. % methylmorpholine-N-oxidesolution and about 60.0 wt. % methylmorpholine-N-oxide solution.
 4. Themethod of claim 1, wherein the methylmorpholine-N-oxide reacts with thehydrogen sulfide in the presence of iron.
 5. The method of claim 4,wherein the iron comprises a hydrated rust, a hydrated ferrous salt, orany combinations thereof.
 6. The method of claim 1, wherein the heat isprovided by subterranean heat.
 7. The method of claim 6, wherein themethylmorpholine-N-oxide solution comprises a temperature, and whereinthe temperature of the methylmorpholine-N-oxide solution increases byabout 1.6° F. for about every 100 feet downhole.
 8. The method of claim1, wherein adding heat comprises increasing the temperature of themethylmorpholine-N-oxide solution to a temperature between about 40° C.and about 75° C.
 9. The method of claim 1, wherein themethylmorpholine-N-oxide solution is exposed to the sour liquid fromabout 24 hours to about 48 hours.
 10. The method of claim 1, furthercomprising contacting the methylmorpholine-N-oxide solution with a sourgas.
 11. The method of claim 1, wherein the sour liquid comprises oil.12. The method of claim 1, wherein the hydrogen sulfide is removed byoxidation.
 13. The method of claim 12, wherein oxidation of the hydrogensulfide produces elemental sulfur.
 14. The method of claim 13, furthercomprising treating the elemental sulfur.
 15. The method of claim 1,further comprising a mole ratio of methylmorpholine-N-oxide to hydrogensulfide between about 1:1 and about 5:1.
 16. The method of claim 1,further comprising a mole ratio of methylmorpholine-N-oxide to hydrogensulfide between about 1:1 and about 3:1.
 17. The method of claim 1,further comprising a mole ratio of methylmorpholine-N-oxide to hydrogensulfide of about 2:1.
 18. The method of claim 1, wherein adding themethylmorpholine-N-oxide solution to the sour liquid comprises injectingthe methylmorpholine-N-oxide solution downhole.
 19. The method of claim18, wherein the injecting comprises injecting themethylmorpholine-N-oxide solution with steam.
 20. The method of claim18, wherein the injecting comprises injecting into a drilling fluid.